Process for the preparation of nylon block polymers

ABSTRACT

A process for preparing a nylon block copolymer which comprises bringing into reactive contact lactam monomer, basic lactam polymerization catalyst and a composition containing one or more lactam functional materials selected from the group represented by the formula: ##STR1## wherein, Q is ##STR2## with Y=C 3  -C 11  alkylene; b is an integer equal to 2 or more; 
     R 1  is an alkyl, aryl, aralkyl, alkyloxy, halogen, aryloxy, or aralkyloxy group; 
     Z is a segment of: (1) a polyether, provided said polyether is not solely polyarylene polyether; (2) a polyester containing polyether or polymeric hydrocarbon segments (3) a hydrocarbon; (4) a polysiloxane; or (5) combinations thereof.

RELATED REFERENCES

This is a continuation of application Ser. No. 467,625, filed Feb. 18,1983, now abandoned, which is a continuation-in-part of U.S. patentapplication Ser. No. 374,853 filed May 4, 1982, now abanoned, which is acontinuation of Ser. No. 274,331, filed June 16, 1981, now abandoned.

FIELD OF THE INVENTION

This invention relates to lactam functional materials and compositioncontaining the same which can be employed in the preparation of nylonblock polymers.

DESCRIPTION OF THE PRIOR ART

Polymers containing polyamide segments and segments of another materialhave been disclosed in the art and are herein referred to as "nylonblock polymers". A combination of polyamide segments and segments ofanother polymeric material allows for the obtaining of block polymerswith unique combinations of properties. The properties can be varied byvarying the polyamide and/or other polymeric segments in the blockpolymer. Such block polymers have been found particularly suitable foruse as fibers, fabrics, films and molding resins.

In U.S. Pat. No. 4,031,164, issued June 21, 1977, and No. 4,223,112,issued Sept. 16, 1980, both to Hedrick and Gabbert, there are taughtnylon block polymers containing nylon segments derived from lactammonomers and other polymeric blocks derived from polyols. Polyacyllactams provide linkages for blocks in the nylon block polymers taughtin Hedrick and Gabbert. Molded articles having a unique combination ofproperties can be made from the nylon block polymers taught therein.

It is taught in the aforementioned Hedrick and Gabbert patents that thepreparation of the block polymers taught therein involves mixingtogether lactam monomer, polyol, lactam polymerization catalyst and thepolyacryl lactam. The process described in the above referred to Hedrickand Gabbert patents for making nylon block copolymers typically resultsin the formation of some polyamide homolog due to the polyacyl lactamswhich are acyllactam containing materials, as hereinafter defined,reacting solely with lactam monomer. It is preferable to minimize anyhomolog since it generally causes detrimental effects such as thereduction of molding impact properties of the nylon block copolymer. Thecatalytic process for imide-alcohol condensation taught by Hedrick andGabbert in U.S. Pat. No. Re 30,371, reissued Aug. 12, 1980, can beemployed in the preparation of the Hedrick and Gabbert nylon blockpolymers. It should be noted that by this process the reaction pathsshown in columns 3 and 4 of U.S. Pat. No. 2,682,526 issued June 29,1954, to Flory occur thus resulting in the preparation of multipleacyllactams functional materials species, (hereinafter defined).Furthermore, reacting a polyol and polyacyl lactam in accordance withthis process results in a mixture containing residual catalyst thatshould be removed or inactivated to reduce the potential difficulties inany subsequent preparation of nylon block copolymer moldings from saidmixture.

In U.S. Pat. No. 3,657,385, issued Apr. 18, 1972 to Matzner et al, thereare disclosed block polymers prepared from lactam monomer andpolyarylene polyethers by anionically polymerizing the lactam monomerwith a catalyst-initiator system which comprises, as the initiator oractivator, one or more of certain polyarylene polyethers. The particularpolyarylene polyether initiators disclosed as useful have terminalgroups selected from various specified groups.

Alternative methods for the preparation of nylon block polymers, forexample, of the type taught in the aforementioned Hedrick and Gabbertpatents, would be of interest to those skilled in the art and is anobject of the present invention. Another object of this invention is toprovide new materials useful as intermediates in the preparation ofnylon block polymers. These and other objects will become apparent fromthe following detailed description of the present invention.

SUMMARY OF THE INVENTION

In accordance with the present invention, there is provided a processfor preparing a nylon block polymer which comprises bringing intoreactive contact lactam monomer, basic lactam polymerization catalystand lactam functional materials selected from the group consisting ofthose of the formulae: ##STR3## wherein, ##STR4## with Y=C₃ -C₁₁alkylene; b is an integer equal to 2 or more;

R₁ is an alkyl, aryl, aralkyl, alkyloxy, halogen, aryloxy, or aralkyloxygroup;

Z is a segment of: (1) a polyether, provided said polyether is notsolely polyarylene polyether; (2) a polyester containing polyether orpolymeric hydrocarbon segments (3) a hydrocarbon; (4) a polysiloxane; or(5) combinations thereof.

DETAILED DESCRIPTION OF THE INVENTION

The acid halide functional materials taught herein can be prepared byreacting a hydroxyl-containing material with an acid halide functionalmaterial containing two or more carboxylic acid halide groups (i.e.##STR5## halogen groups). In the reaction mixture the equivalents ofacid halide groups should be maintained in excess of the hydroxylgroups. In this reaction the acid halide material attaches to thehydroxyl sites in the hydroxyl-containing material through esterlinkages. By-product hydrogen halide results from the hydrogen andhalogen which are displaced. An example of this reaction can be depictedas follows: ##STR6## wherein my≧nx+2

In the above reaction R'--OH)_(x) is a material containing two or morehydroxyl groups, i.e. x is at least 2, preferably 2 to 4. This materialcan be a diol, triol or a material having higher hydroxyl content. TheR' group in the hydroxyl-containing material can be a hydrocarbon(preferably having a molecular weight of at least 100), a polyether or apolysiloxane group.

It is to be understood that, unless otherwise stated, reference hereinto "molecular weight" for polymers or polymeric segments means numberaverage molecular weight which can be determined by methods well knownin the art, e.g. gel phase chromatography.

Reference herein to "polysiloxane" group or segment herein means a groupor segment containing at least 50 percent by weight of one or more##STR7## (a siloxane unit) repeat units. In this structure for siloxaneunits A can be methyl or phenyl. Polysiloxane groups or segments wouldtypically have present other groups, for example, ether groups withresidues of lower alkyls such as ethane, such groups typically beingterminating groups on a chain of repeating siloxane units. These othergroups may comprise up to 50 weight percent of the polysiloxane group,preferably less than 30 weight percent.

Preferred R' groups are hydrocarbon and polyether group. Exemplaryhydrocarbon groups are alkylene in the case of diols such as ethyleneglycol and polymeric hydrocarbons such as a segment of polybutadienewhich can be functionalized to contain two or more hydroxyl groups. Apolyoxypropylene segment which can be functionalized to contain two ormore hydroxyl groups is an example of a polyether group.

Exemplary hydroxyl-containing materials useful in the above depictedreaction are ethylene glycol, propylene glycol, poly(oxybutylene)glycol, poly(oxyethylene) glycol, poly(oxypropylene) diol,poly(oxypropylene) triol, poly(oxypropylene) tetrol, polybutadiene diol,hydroxyl-functionalized polydimethylsiloxanes and combinations thereof,for example, block polymers of poly(oxypropylene) and poly(oxyethylene)functionalized with two or more hydroxyl groups.

The acid halide material in the above-depicted reaction, i.e. ##STR8##contains two or more acid halide groups, i.e. y is greater than 1,generally 2, 3 or 4, preferably 2. The R group in this acid halidematerial is a hydrocarbon group or a hydrocarbon group containing etherlinkages (generally up to 20 weight percent ether oxygen). Preferred arehydrocarbon groups, most preferably those containing 1 to 12 carbonatoms. Even more preferred R groups are hydrocarbon groups orhydrocarbon groups having ether linkages either of which provide atleast three successively bonded elementary atoms between any twocarbonyl groups bonded to R. Examples of preferred acid halides aresebacic acid chloride and phthalic acid chloride wherein the carbonylgroups are attached thereto either in the meta- or para-position, i.e.isophthaloyl and terephthaloyl acid chloride, respectively.

In place of the acid halide depicted in the above reaction there may beemployed acid halides having the structure ##STR9## In the abovedepicted structure X is halogen.

In yet another embodiment of the teachings herein, in place of the acidhalides described above as useful in the above reaction, there may beemployed acid halides having the structure ##STR10## or even phosphorusor sulfur-containing acid halides of the structures ##STR11## with X asdefined hereinbefore, and R₁ being an alkyl, aryl, aralkyl, halogen,alkyloxy, aryloxy or aralkyloxy group.

Exemplary acid halides which may be employed in the above reaction areadipoyl chloride, terephthaloyl chloride, trimesoyl chloride,trimellitic chloride, oxalyl chloride, isophthaloyl chloride,pyromellitoyl chloride, pimeloyl chloride, glutaryl chloride,benzophenone tetracarboxylic acid chloride, oxydiacetyl chloride,oxydibenzoyl chloride, sulfuryl chloride, phosphorus oxychloride,sebacic acid chloride, azelaic acid chloride, alkyl-, aryl-, andaralkylphosphorodichloridates, alkyl-, aryl- andaralkylphosphonodichloridates.

It is to be understood that numbers designating the amount of functionalgroups on materials described herein (e.g. the numbers x, y and b above)would be integers for a single molecule of the material. However, manyof such materials, particularly polymeric materials, generally exist inmixtures or compositions containing species having varying amounts offunctionality, some species possibly having an amount higher or lowerthan desired. For such mixtures or compositions, a number designatingthe amount of functional groups would represent an average of thedifferent species and thus would not necessarily be an integer.

Essentially all of the hydroxyl groups in the hydroxyl-containingstarting material are converted in the above described reaction. Byproviding the acid halide groups in excess of the hydroxyl groups theresulting reaction product is functionalized with acid halide groups.

The above reaction is preferably carried out in the presence of anon-interfering solvent, e.g. cyclohexane, toluene, tetrahydrofuran, oracetone to facilitate removal of the hydrogen halide which is generated.It is also possible for the reaction to proceed without the presence ofa solvent with the hydrogen halide being driven off with heat, vacuum,nitrogen sweeping or the like. When a solvent is employed in thereaction, a basic material which acts as an acid scavenger to produce aby-product which is insoluble in the solvent may be employed as aconvenient means for removing the hydrogen halide. Well known acidscavengers such as tertiary amines may be employed. The above reactioncan be carried out under essentially ambient conditions and will proceedeven more rapidly at higher temperatures, e.g. 30° to 150° C. Precisetemperature for the reaction may depend upon the solvent employed. If asolvent is employed it can be removed after the reaction bydistillation.

The above-described procedure results in reaction between ahydroxyl-group of the hydroxyl-containing material and an acid halidegroup of the acid halide material. The following acid halidefunctionalized materials can thus be prepared: ##STR12## wherein, X ishalogen;

a is an integer equal to 1, 2 or 3;

b is an integer equal to 2 or more;

R is a di- or poly-valent group selected from hydrocarbon groups andhydrocarbon groups containing ether linkages;

Z is a segment of (1) of polyester, provided said polyester is notcomprised solely of poly(tetramethylene terephthalate) orpoly(tetramethylene isophthalate); (2) a polyether; (3) a hydrocarbon;or (4) a polysiloxane.

The following acid halide-functionalized materials representing yetanother embodiment of the teachings herein can also be prepared inaccordance with the above-described procedure: ##STR13## wherein, R₁ isan alkyl, aryl, aralkyl, halogen, alkyloxy, aryloxy, or aralkyloxygroup;

X and b are as defined hereinbefore; and

Z is a segment of (1) a polyester; (2) a polyether, provided saidpolyether is not solely polyarylene polyether; (3) a hydrocarbon; or (4)a polysiloxane.

The Z segment in the above Formulae I(a) and I(b) is a segment of (1) apolyester; (2) a polyether; (3) a hydrocarbon; or (4) a polysiloxanewith certain provisos recited hereinbefore. The Z segment for thereaction product depicted by Formulae I(a) and I(b) can be the same asan R' group of a hydroxyl-functional material employed in the reactiondescribed hereinbefore. Alternatively, the Z segment can be a segmentcontaining two or more residues of the starting hydroxyl-containingmaterial linked together with a residue(s) of the starting acid halidematerial.

Reference herein to "acid halide functional materials" means compoundsrepresented by formulas (I(a) and (b)).

It is to be understood that in connection with the description of Zsegments or R' groups herein, reference to polymeric segments/groupsembraces oligomeric segments/groups unless a specific usage precludessuch interpretation. It is also to be understood that thesesegments/groups may be linear, branched or even star structures.

A Z segment which is a segment of a polyester could be derived from thereaction of an acid halide having di- or multi-halide functionality witha hydroxyl-containing material, the groups in the hydroxyl-containingmaterial being linked together by the acid halide through polyesterlinkages. Exemplary hydroxyl-containing starting materials which may beemployed in such a reaction are ethylene glycol, propylene glycol,polycaprolactone diol and polyol, and polybutadiene diol. Acid halidessuch as those exemplified hereinbefore may be employed. Those skilled inthe art would recognize a wide variety of polyester segments which mayrepresent Z in the above Formulae I(a) and I(b). In the embodimentrepresented by Formula I(a) there are excluded polyester segmentscomprised solely of poly(tetramethylene terephthalate) orpoly(tetramethylene isophthalate).

It should be understood that a Z segment which is a segment of apolyester would in fact contain smaller segments which fall within theother categories of possible Z segments, for example, hydrocarbon orpolyether segments. As an example, a Z segment which is a segment of apolyester can be derived from a hydroxyl-containing material containinga polyether group and an acid halide material whereby two or more of thepolyether groups become linked together by the acid halide materialthrough ester linkages. The hydroxyl-containing material may be derivedfrom a diol, triol, or polyol. A specific example of such would be thereaction product of poly(oxypropylene) triol and terephthaloyl chloridewherein a residue of the terephthaloyl chloride provides a linkagebetween two units derived from the triol. Such polyester Z segmentscould be more specifically described as poly(ether-ester) segments whichare a preferred type of polyester segment within the scope of theteachings herein.

Similarly, other preferred polyester Z segments are those which are thereaction product of a diol or triol which contains polymeric hydrocarbonunits with an acid halide material whereby two or more of the polymerichydrocarbon units become linked together by the acid halide material. Anexample of such is the reaction product of a polybutadiene diol withterephthaloyl chloride wherein two or more polybutadiene segments arelinked together by the terephthaloyl chloride through ester linkages.

Polyester segments which may represent Z can vary widely in size butgenerally have molecular weights of at least 500. Preferred molecularweights for these segments are from about 1,000 to about 25,000.Preferred types of polyesters which contain polyether or polymerichydrocarbon segments generally contain these segments at molecularweights of from about 500 to about 4,000.

Furthermore, as will be discussed below, the properties of a nylon blockcopolymer prepared from an acid halide functionalized material whereinthe Z segment is a polyester exhibits unexpected results when thepolyester contains polyether segments having a minimum molecular weightof about 2,000.

A segment of a polyether is a preferred Z segment in the presentinvention. Such can be derived from a hydroxyl-containing material whichcontains a polyether segment. Such hydroxyl-containing materials whichare preferred include poly(oxyethylene) glycol; poly(oxybutylene)glycol; poly(oxypropylene) diol, triol, and tetrol; and block polymersof poly(oxypropylene) and poly(oxyethylene) functionalized with two ormore hydroxyl groups.

The Z polyether segments generally have a molecular weight of at least500, preferably at least 1,000, and more preferably at least about2,000. Preferred molecular weights are from about 1,000 to about 25,000,more preferred 2,000-25,000. Even more preferred are molecular weightsfrom about 2,000 to about 4,000 for diol derivatives, from about 3,000to about 12,000 for triol derivatives and from about 4,000 to about16,000 for tetrol derivatives.

It has been determined, as will be further discussed below, that theproperties of a nylon block copolymer prepared from an acid halidefunctionalized material wherein the Z segment is a polyether can besignificantly influenced by the molecular weight of the segment and thatcertain preferred molecular weights result in unexpected beneficialresults.

It has further been determined that a minimal amount of cross-linking inthe prepared nylon block copolymer, which occurs when the averagefunctionality of a composition of acid halide functional materials isgreater than two, also results in unexpectedly improved properties.These features will be discussed and exemplified more fully below.

In the embodiment represented by Formulae I(b) are excluded Z segmentswhich are solely polyarylene polyether, i.e. segment consistingessentially only of units of the Formula [O--AR--O--AR] wherein AR is abenzenoid residue (mono-, di- or poly-nuclear) bonded to the etheroxygens through aromatic carbons.

A Z segment which is a segment of a hydrocarbon can be derived from ahydroxyl-containing material which contains a hydrocarbon segment. Thesize of the hydrocarbon group can vary widely in size from alkylenegroups of low molecular weight to polymeric hydrocarbons ofsubstantially higher molecular weight. If Z is a low molecular weighthydrocarbon the acid halide-functional materials of Formulae I(a) andI(b) could be employed to join nylon blocks together as describedhereinafter. The resulting linkage would introduce the low molecularweight hydrocarbon as an additional block in the resulting nylon blockpolymer. Examples of low molecular weight hydrocarbon (Z) segments wouldbe the C₂ to C₇ alkylenes.

Preferred Z segments in the present invention are segments of polymerichydrocarbons. By "polymeric hydrocarbon segment" herein is meant ahydrocarbon segment of molecular weight of at least about 100 andcontaining two or more repeat units. Exemplary hydroxyl-containingmaterials which can be employed to provide Z segments which are segmentsof a polymeric hydrocarbon are alkylene (C₈ and above) glycols andpolybutadiene diols, triols, tetrols and even higher polyols. Segmentswhich are polymeric hydrocarbons preferably have a molecular weight ofat least 500, even more preferably from about 1,000 to about 25,000.Most preferred are molecular weights from about 1,000 to about 4,000 fordiol derivatives, from about 3,000 to about 12,000 for triolderivatives, and from about 4,000 to about 16,000 for tetrolderivatives.

The Z segment may also be a segment of a polysiloxane, such beingdefined hereinbefore. Such a Z segment could be derived from ahydroxyl-containing material having a polysiloxane segment. Exemplaryhydroxyl-containing materials of this type are polydimethylsiloxanescontaining two or more hydroxyl functional groups. Polysiloxane segmentswould generally have a molecular weight of at least 500, preferably atleast 1,000. More preferably the molecular weight of such segments wouldbe from about 1,000 to about 25,000.

It should be recognized that the Z segment in the above Formulae maycontain a combination of the just described polyester, polyether,hydrocarbon and polysiloxane segments. As discussed hereinbeforepreferred polyester segments contain polyether or polyhydrocarbonsegments. Also as discussed hereinbefore, polysiloxane segments asdefined herein typically contain groups other than siloxane units. It isrecognized that other combinations of polyester, polyether, hydrocarbonand polysiloxane segments are possible, and such are contemplatedequivalents for use as Z segments in the present invention.

In the above Formulae I(a) and I(b), X is a halogen, preferably chlorineor bromine, most preferably chlorine. The integer a in Formulae I(a) ispreferably 1 which would be the case when a diacid halide of thestructure ##STR14## is employed in the reaction described above. Theinteger b in Formulae I(a) and I(b) is at least 2, preferably 2 to 20,most preferably 2 to about 4. R in the above Formulae I(a) is a di- orpoly-valent hydrocarbon group (valency equal to a+1) and wouldcorrespond to the R group in the acid halide starting material in theabove described reaction scheme. R₁ in Formulae I(b) is an alkyl, aryl,aralkyl halogen, alkyloxy, aryloxy, or aralkyloxy group.

Acid halide functional materials of the present teachings which arepreferred are those represented by the formula: ##STR15## wherein X ischlorine or bromine, b is 2 to about 4 and R and Z are as definedhereinabove. As discussed hereinabove, a further preferred form for acidhalide functional materials is wherein the R groups provide at leastthree successively bonded elementary atoms between any two carbonylgroups bonded to R. Examples of such R groups are those derived fromadipoyl halide, isophthaloyl halide and terephthaloyl halide.

The acid halide functional materials taught herein have been found to beuseful in the preparation of nylon block polymers. It has been foundthat the acid halide functional materials of the present invention canbe reacted with a lactam monomer to result in an lactam functionalmaterial which can further be reacted with lactam monomer to form anylon block polymer. For example, the acid halide functional materialsdepicted in Formulae I(a) above can be reacted with a lactam monomercontaining from about 4 to about 12 carbon atoms, to produce thefollowing acyllactam functional materials: ##STR16## with Y=C₃ -C₁₁alkylene; and a, b, R and Z are as defined above for Formula I(a).

Similarly, the acid halide functional materials depicted in FormulaeI(b) above can be reacted with lactam monomer to produce the followinglactam functional materials: ##STR17## with Y=C₃ -C₁₁ alkylene; and b,R₁ and Z are as defined above for Formula I(b), with R₁ also possiblybeing Q.

Reference herein to "lactam functional materials" means compounds havingacyllactam groups wherein (1) an ether oxygen is linked to a diacidhalide residue as generally shown in formulas III(a) and III(b) and/or(2) wherein a lactam residue (--NH--Y--CO--) is positioned between theether oxygen and the acid halide residue. The lactam functionalmaterials of the present invention are those shown in formulas III(a)and III(b). Reference herein to "lactam containing materials" includesacyllactam functional materials as defined above and also compoundswhich do not contain an ether oxygen such as certain polyacyl lactamsdescribed in the above referred to Hedrick et al patents.

The reaction of acid halide functional materials with lactam monomer toprepare the lactam functional materials of Formulae III(a) and III(b)would typically be carried out in the presence of a solvent, e.g.,cyclohexane, toluene, acetone or excess lactam monomer, and an acidscavenger to facilitate the removal of hydrogen halide generated in thereaction. The reaction may also be carried out without the presence of asolvent. The previous discussion regarding the use of solvent andreaction conditions in connection with the reaction ofhydroxyl-containing material with acid halide functional materialequally applies here. In an alternative method the acyllactam functionalmaterials can be prepared under similar conditions from a reactionmixture containing a hydroxyl-containing material, an acid halidefunctional material and lactam monomer, without ever isolating theintermediate acid halide functional material (Formulae I(a) or I(b))which is formed. The preparation of the lactam functional materials ofthe present invention by a method without employing the basicpolymerization catalyst generally taught by Hedrick and Gabbert asdiscussed hereinbefore eliminates the potential for unwanted catalyticreaction between the lactam functional material and lactam monomer andthere is no necessity to carry out an additional step of deactivating orremoving residual catalyst. A quantitative reaction is preferred todisplace essentially all of the halogens in the acid halide of FormulaeI(a) or I(b) with lactam groups.

The lactam functional polymer of Formulae III(a) and (b) above can thenbe reacted with additional lactam monomer to prepare a nylon blockpolymer. An advantage of preparing nylon block copolymers from thelactam functional materials of the present invention is the lessenedpotential of forming polyamide homologs which may be associated withprior art methods. The polyamide homolog typically results from thereaction between lactam monomer and lactam-containing materials such asbisimides. Additional hydroxyl-containing material may be included inthe reaction mixture but the acyllactam groups should be present inexcess of the hydroxyl groups in the mixture. The hydroxyl-containingmaterial will become incorporated in the nylon block polymer. Thematerials should be intimately mixed. Antioxidant is generally includedin the reaction mix. This reaction is generally carried out in thepresence of a suitable basic catalyst for the anionic polymerization oflactam, preferably caprolactam magnesium bromide or chloride. A smallamount of catalyst may be effective, e.g. a fraction of one mole percentof the lactam monomer to be polymerized, but higher amounts, e.g. from 1to 20 mole percent, or higher, based on the lactam monomer may beemployed. The lactam monomers generally contain 4 to about 12 carbonatoms, preferably 6 to about 12. Caprolactam (which herein meansε-caprolactam) is particularly preferred. Corresponding residues of suchpreferred lactam monomers are preferred for Q in Formulae III(a) and(b). In relatively short reaction times, e.g., less than 10 minutes oreven less than 30 seconds, and under moderate conditions, e.g. fromabout 70° C. to about 250° C., preferably about 120° C. to about 170°C., the formation of a nylon block polymer results. The lactam canpolymerize at the lactam sites and also be inserted as ester and amidesites. Nylon block polymers disclosed in the aforementioned Hedrick andGabbert patents can thus be prepared. The fast reaction time to form thenylon block polymers makes the materials disclosed herein particularlyuseful in reaction injection molding applications, with other relatedapplications, such as in-mold coating of substrates, rotation molding,resin transfer molding, and pultrusion molding also contemplated.

The relative amounts of lactam monomer and lactam functional polymeremployed in the preparation of nylon block polymer by the processdescribed above can vary widely depending upon the nylon block polymerdesired. The lactam monomer and lactam functional polymer can be presentin proportions ranging up to 99 parts by weight of either component to 1part by weight of the other. Preferred amounts are from about 60 toabout 90 percent by weight lactam monomer and from about 10 to about 40percent by weight lactam functional polymer. However, from about 40 toabout 70 percent by weight lactam functional polymer can be employed tomake elastomeric block polymers. Under typical reaction conditions thepolymerization is essentially quantitative, i.e. essentially all of thelactam and lactam functional polymer is incorporated in the nylon blockpolymer.

In the preparation of nylon block polymers it may be desirable toconduct the polymerization reaction in the presence of one or more othermaterials conventionally incorporated in nylon block polymers. Suchmaterials would include fillers, plasticizers, flame retardants,stabilizers, fibrous reinforcing agents such as asbestos and glassfiber, dyes and pigmenting materials. Such materials may be introducedin the materials of Formulae I(a), (b) or III(a), and (b), taughtherein, or otherwise.

The following examples will illustrate the present invention in greaterdetail. These examples are for illustrative purposes only and are not tobe construed as limiting the scope of the invention which would includevarious other modifications. Unless otherwise indicated herein, allparts, percentages, ratios and the like are by weight.

EXAMPLE 1 A. Preparation of Acid Halide Functional Material

A solution of 48.2 grams (0.049 equivalents) Pluracol GP-3030(polyoxypropylene triol, Mol. Wt. about 3,000) in 40 cc. toluene wasrefluxed to remove essentially all water by azeotrope. The mixture wascooled to room temperature, and 9.45 grams (0.103 equivalents) of crudeadiproyl chloride was added. The solution was heated to reflux. Duringreflux hydrogen chloride gas was evolved rapidly. The mixture wasrefluxed one hour.

This reaction resulted in the hydroxyl sites of the polyoxypropylenetriol being functionalized by the adipyl chloride to form the tri (acidchloride) functional derivative.

B. Preparation of Acyllactam Functional Material

To the resulting reaction product prepared in A. above was added 169milliliters (mls.) dry molten caprolactam. The mixture was refluxed.Reflux pot temperature rose to 185° C. Hydrogen chloride evolutionoccurred at a moderate rate. The course of reaction was monitored byperiodic determination of residual acidity. After one and one-half hoursreflux at 185° C., acidity was 0.077 milli-equivalents/gram (meq./gm.).The solution was cooled and was allowed to set overnight. An additional45 mls. toluene was added and the solution again refluxed--this time at140° pot temperature. After two hours additional reflux (total refluxtime=three and one-half hours) acidity was 0.042 meq./gm. when titratedto phenolphthalein end point with 0.1 normal sodium hydroxide.Additional reflux period of three and one-half hours did not change thisacidity.

This reaction resulted in the chlorine atoms in the product prepared inA. being displaced by caprolactam groups to form the tri(acyllactam)functional derivative.

C. Preparation of Nylon Block Polymer

To the reaction product prepared in B. above an additional 11.8 gramsPluracol GP-3030 were added. Toluene was stripped off under vacuum, andthen 25 cc. caprolactam removed by distillation. The resulting solutionwas cooled to 75° C. and 84 mls. of 0.4 molar bromomagnesium caprolactam(in caprolactam) was injected under vacuum. The mixture was stirredvigorously for 20 seconds, the vacuum released to nitrogen and themixture poured into a 130° C. Teflon-lined mold. The material was setinto a firm polymer in two minutes. After an additional two minutes thepolymer was removed from the mold and cut into specimens for physicaltesting. The resulting polymer was a nylon block copolymer whichcontained about 20% poly(oxypropylene) and which exhibited the followingproperties (determined in accordance with the procedures describedhereinafter for Examples 29-51):

    ______________________________________                                        Tensile Strength  5960 (psi) 41 MPa                                           Tensile Elongation                                                                              30%                                                         Tear Strength     1280 (pli) 224 × 10.sup.3 N/m                         Flexural Modulus  157,000 (psi) 1082.5 MPa                                    Notched Izod Impact                                                                             6.6 (ft. lbs./in). 352 J/m                                  ______________________________________                                    

The following polyols and acid halides were employed in the preparationof additional acid halide functional polymers, acyllactum functionalpolymers and nylon block polymers:

                  TABLE A                                                         ______________________________________                                        Polyols                                                                       Designation      Description                                                  ______________________________________                                        Niax 11-34 (NIAX)                                                                              Ethylene Oxide capped                                                         poly(oxypropylene) triol                                                      (Molec. Wt. about 4,800).                                    Pluracol P-380 (P380)                                                                          Poly(oxypropylene) triol                                                      (Molec. Wt. about 6,760).                                    Pluracol GP 3030 (GP)                                                                          Poly(oxypropylene) triol                                                      (Molec. Wt. about 3,000).                                    Pluracol P494 (P494)                                                                           Poly(oxypropylene) tetrol                                                     (Molec. Wt. about 4,750).                                    Carbowax 4000 (CARB)                                                                           Poly(oxyethylene) diol                                                        (Molec. Wt. about 3,700).                                    R 45 M (R45)     Poly(butadiene) diol (Molec.                                                  Wt. about 2,800).                                            Polyol Mix (MIX) 50/50 by mole mixture of                                                      Niax 11-34 and GP 3030                                       Q4-3667 (Q4)     Silicone polycarbinol.                                       Tetrol 9000 (TET 9)                                                                            Ethylene Oxide capped                                                         poly(oxypropylene) tetrol                                                     (Molec. Wt. about 9,000).                                    Triol 8000 (TRI 8)                                                                             Ethylene Oxide capped                                                         poly(oxypropylene) triol                                                      (Molec. Wt. about 8,000).                                    ______________________________________                                    

                  TABLE B                                                         ______________________________________                                        ACID HALIDES                                                                                       Designation                                              ______________________________________                                        Terephthaloyl Chloride TERE                                                   Adipoyl Chloride       ADIP                                                   Isophthaloyl Chloride  ISOP                                                   ISOP/TERE              ISO/TER                                                Mixture (50/50 Wt. %)                                                         Oxydibenzoyl Chloride  OBC                                                    Phenylphosphonyl Chloride                                                                            PPC                                                    Sulfuryl Chloride      SC                                                     Phosphorus Chloride    POC                                                    Oxalyl Chloride        OXA                                                    ______________________________________                                    

EXAMPLE 2 Preparation of Acid Halide Functional Material

A solution of 96.0 grams (0.02 mole) of Niax 11-34 in 237 mls. ofcyclohexane was dried by removing 27 mls. of the water azeotrope duringa half-hour reflux period. The solution was cooled to 21° C. and 12.18grams (0.06 mole) of terephthaloyl chloride (TERE) were added withstirring. A solution of 6.08 grams (0.06 mole) of triethylamine in 20milliliters of cyclohexane was added over 5 minutes. The temperaturerose from 21° C. to 26° C., and a white precipitate formed. The solutionwas heated to reflux and was cooled immediately to 10° C. and filteredthrough "Celite". Removal of the solvent under vacuum at 80° C. left102.48 grams of a yellow syrup. The IR spectrum showed ester and acidchloride carbonyl absorption at 1745 cm.⁻¹ and 1800 cm.⁻¹, respectively,and no hydroxyl absorption, demonstrating the formation of the desiredacid halide functional polymer.

EXAMPLE 3 A. Preparation of Acid Halide Functional Material

A solution containing 48.0 grams (0.01 mole) of Niax 11-34 in 77 mls. ofcyclohexane was dried by removing 27 mls. of the water azeotrope duringa half-hour reflux. The polyol solution was cooled to 50° C., and 6.09grams (0.03 mole) of solid terephthaloyl chloride (TERE) were added withstirring. A solution of 3.04 grams (0.03 mole) of dry triethylamine in20 mls. of cyclohexane was added over a period of 10 minutes. Thetemperature rose from 47.5° C. to 49° C. The resulting creamy slurry wasstirred and heated at reflux for a half-hour to complete formation ofthe acid halide functional polymer.

B. Preparation of Acyllactam Functional Material

The reaction mixture from A. above was cooled to 42° C. and 4.0 grams(0.035 mole) of solid caprolactam were added with stirring. A solutionof 3.54 grams (0.035 mole) of triethylamine in 20 mls. of cyclohexanewas added over a period of seven minutes. The temperature rose 42° C. to53° C. An additional 60 mls. of cyclohexane were added, and the mixturewas heated at reflux with stirring for a half-hour. Cooling to 11° C.and filtration through "Celite" left a clear, colorless filtrate.Removal of the solvent at 80° C. under vacuum for three hours yielded52.26 grams of a clear, yellow syrup. The acidity of the resultingacyllactam functional polymeric material was 0.028 meq./gm.

EXAMPLE 4 Preparation of Acyllactam Functional Material

A solution of 96.0 grams (0.02 mole) of Niax 11-34 and 7.0 grams (0.062mole) of caprolactam in 227 mls. of cyclohexane was dried by refluxingfor an hour, while 27 mls. of the water azeotrope were removed. Thesolution was cooled to 15° C., and 12.18 grams (0.06 mole) ofterephthaloyl chloride (TERE) were added with stirring. A solution of12.66 grams (0.125 mole) of triethylamine in 40 mls. of cyclohexane wasadded over a five minute period. The temperature rose from 15° C. to 30°C., and a white precipitate formed. The mixture was heated to reflux andkept there for one hour; then, 1.5 grams of methanol were added andrefluxing was continued for another hour. The mixture was cooled to 10°C. and was filtered through "Celite". Removal of the solvent undervacuum at 80° C. over three hours left 93.93 grams of an amber syrup.The acidity of the resulting acyllactam functional polymeric materialwas 0.032 meq./gm.

EXAMPLES 5-28

Additional Examples 5-28 were carried out substantially in accordancewith previous Example 3 (A and B) or Example 4 except for the particularmaterials and amounts thereof which were employed. The type and amountsof materials and method of preparation (Ex. 3 or Ex. 4) for each ofExamples 5-28 are shown in Table C. In some of the Examples run inaccordance with Example 3, the reflux in Step B was extended beyond 30minutes, up to 3 hours in some cases. Additionally, in some of theExamples run in accordance with Example 3 a small amount of methanol orof anhydrous sodium carbonate was added after 30 to 60 minutes of refluxin Step B for the purpose of adjusting the acidity of the final product.For some of the Examples run in accordance with Example 4 an equivalentamount of sodium carbonate was used instead of the methanol added duringthe reflux step. The acidity of the resulting acyllactam functionalmaterial was between about 0.028 and 0.3 meq./gm. for each of theseexamples.

                                      TABLE C                                     __________________________________________________________________________                           Caprolactam,                                                                         TEA,                                            Example                                                                            Polyol (Moles)                                                                        Acid Halide (Moles)                                                                     Moles  Moles                                                                             Method                                      __________________________________________________________________________     5   NIAX (0.01)                                                                           TERE (0.03)                                                                             0.031  0.06                                                                              EX. 3                                        6   GP (0.01)                                                                             TERE (0.03)                                                                             0.035  0.065                                                                             EX. 3                                        7   NIAX (0.02)                                                                           TERE (0.06)                                                                             0.062  0.125                                                                             EX. 3                                        8   GP (0.01)                                                                             TERE (0.03)                                                                             0.035  0.065                                                                             EX. 3                                        9   NIAX (0.01)                                                                           ADIP (0.03)                                                                             0.035  0.065                                                                             EX. 3                                       10   NIAX (0.03)                                                                           ISOP (0.06)                                                                             0.062  0.125                                                                             EX. 3                                       11   P494 (0.02)                                                                           ADIP (0.08)                                                                             0.082  0.162                                                                             EX. 3                                       12   P494 (0.015)                                                                          TERE (0.06)                                                                             0.061  0.121                                                                             EX. 3                                       13   NIAX (0.02)                                                                           ISO/TER (0.06)                                                                          0.065  0.125                                                                             EX. 3                                       14   MIX (0.02)                                                                            TERE (0.06)                                                                             0.065  0.125                                                                             EX. 3                                       15   CARB (0.02)                                                                           TERE (0.04)                                                                             0.045  0.085                                                                             EX. 3                                       16   NIAX (0.60)                                                                           TERE (1.80)                                                                             1.95   3.75                                                                              EX. 3                                       17   R 45 (0.042)                                                                          TERE (0.088)                                                                            0.095  0.183                                                                             EX. 3                                       18   TRI 8 (0.02)                                                                          TERE (0.06)                                                                             0.062  0.125                                                                             EX. 4                                       19   P380 (0.02)                                                                           TERE (0.06)                                                                             0.062  0.125                                                                             EX. 4                                       20   TET 9 (0.02)                                                                          TERE (0.08)                                                                             0.082  0.162                                                                             EX. 4                                       21   NIAX (0.02)                                                                           TRIM (0.06)                                                                             0.13   0.18                                                                              EX. 3                                       22   NIAX (0.02)                                                                           OXA (0.06)                                                                              0.062  0.125                                                                             EX. 4                                       23   Q4 (0.06)                                                                             TERE (0.06)                                                                             0.062  0.125                                                                             EX. 4                                       24   NIAX (0.03)                                                                           TERE (0.075)                                                                            0.062  0.155                                                                             EX. 3                                       25   NIAX (0.03)                                                                           PPC (0.09)                                                                              0.091  0.185                                                                             EX. 3                                       26   NIAX (0.03)                                                                           POC (0.09)                                                                              0.182  0.272                                                                             EX. 3                                       27   NIAX (0.03)                                                                           SC (0.09) 0.091  0.185                                                                             EX. 3                                       28   NIAX (0.03)                                                                           OBC (0.09)                                                                              0.091  0.185                                                                             EX. 3                                       __________________________________________________________________________

EXAMPLES 29-51 Preparation of Nylon Block Polymers

Nylon block polymers were prepared from acyllactam functional polymersprepared in Examples 5-28 by either a hand casting polymerization method(HC) or a reaction injection molding polymerization method (RIM). Thesemethods are described below.

A. Hand Casting of Nylon Block Polymers (Examples 29-47)

In a 500 ml. flask equipped with stirrer, thermocouple and nitrogeninlet were charged caprolactam and a prepolymer which was anacyllactam-functional polymer prepared in accordance with one of theearlier Examples 5-28. The specific prepolymer example and the amount ofmaterials employed in each of Examples 29-47 is shown in Table D. Ineach case 1.5 grams of Flectol®H (an antioxidant sold by MonsantoCompany which is polymerized 1,2-dihydro-2,2,4-trimethylquinoline) wasadded to the charge. The mixture was heated under vacuum to distill 25mls. caprolactam and then cooled to 75° C.

Separately prepared was a catalyst solution which was a solution ofbromomagnesium caprolactam in caprolactam. The catalyst solution wasgenerally prepared by adding a solution of 3 molar ethyl magnesiumbromide in diethyl ether to dry caprolactam followed by thoroughdegassing under vacuum. Catalyst solutions of various molarities wereprepared. For example, a 0.5 molar bromomagnesium caprolactam catalystsolution was prepared by adding 17 mls. of 3 molar ethyl magnesiumbromide in diethyl ether to 100 grams of dry caprolactam with degassingas stated above. The molarity of the catalyst solution employed forspecific examples is indicated in Table D.

To the above prepared prepolymer solution was injected a specifiedamount of catalyst solution under vacuum. The specific amount ofcatalyst solution employed for the Examples 29-47 is shown in Table D.After stirring vigorously for fifty seconds the vacuum was released tonitrogen and the catalyzed mixture was poured into a Teflon-lined moldheated to 130° C. After 5 to 15 minutes in the mold the resulting solidnylon block polymer was removed. The polymerization of the prepolymerand caprolactam was essentially quantitative in the formation of thenylon block polymer. Specimens were cut for testing.

                  TABLE D                                                         ______________________________________                                        HC EXAMPLES                                                                             Amounts - Grams                                                                             Catalyst                                              Exam- Prepolymer                                                                              Pre-                     Amt.,                                ple   Example   polymer  Caprolactam                                                                            Molarity                                                                             mls.                                 ______________________________________                                        29     5        46.2     148      0.5    35                                   30     6        33.7     173      0.5    30                                   31     7        74       101      0.5    30                                   32     8        30.4     114      0.5    26                                   33     9        53.1     176      0.5    36                                   34    10        44.4     138      0.5    38                                    35*  10        44.4     138      0.5    38                                   36    11        76.8     229      0.5    40                                   37    12        59.05    148      0.5    56                                   38    13        94.65    260      0.5    83                                   39    14        75.7     300      0.5    45                                   40    15        55.8     173      0.5    32                                   41    16        60       196      0.5    30                                   42    21        62       178      0.5    35                                   43    22        55       165      0.5    55                                   44    23        61       134      0.5    80                                   45    24        55.8     169      0.6    50                                   46    25        57       148      0.6    70                                   47    26        59       149      0.6    67                                   ______________________________________                                         *Example 35 also contained 71 gms. P117B 1/16" milled glass fiber which       resulted in a 25% (wt.) glass reinforced nylon block polymer.            

B. Reaction Injection Molding of Nylon Block Polymers (Examples 48-51)

In a 500 ml. flask equipped with stirrer, thermocouple and nitrogeninlet were charged caprolactam and a prepolymer which was an acyllactamfunctional polymer prepared in accordance with earlier Examples 5-29.The specific prepolymer example and the amount of materials employed inpreparing the prepolymer solutions in each of Examples 48-51 is shown inTable E. To each charge was added 1.5 grams of Flectol® H. The mixturewas dried by heating under vacuum to distill 25 mls. caprolactam andthen cooled to 75° C.

Separately a catalyst solution consisting of bromomagnesium caprolactamin caprolactam was prepared by adding a solution of 3 molar ethylmagnesium bromide in diethyl ether to dry caprolactam followed bythorough degassing under vacuum. For example, a 0.26 molarbromomagnesium caprolactam catalyst solution was prepared by adding 17mls. of 3 molar ethyl magnesium bromide in diethyl ether to 200 grams ofdry caprolactam. Catalyst solutions of varying molarities were employedin the Examples as indicated in Table E.

A reaction injection molding was made by pumping the above solutionsinto a closed mold heated to 130° C. Equal amounts by volume of theprepolymer solution and the catalyst solution were combined by means ofgear pumping, except for Example 48 in which the prepolymer solution andcatalyst solution were combined by the same means in a ratio of of 3.4:1by volume (prepolymer solution:catalyst solution). Mixing of thecombined stream prior to injection into the mold was performed by meansof an in-line 6 inch by one-quarter inch Kenics static mixer. The moldwas filled with the mixture and the resulting solid nylon block polymerwas removed from the mold at about 2 minutes after the start ofinjection. The polymerization of the prepolymer and caprolactam wasessentially quantitative in the formation of the nylon block polymer.Specimens were cut for testing.

                  TABLE E                                                         ______________________________________                                        RIM EXAMPLES                                                                              Amounts Charge                                                                Prepolymer Solution                                                      Prepolymer Prepolymer                                                                              Caprolactam                                                                             Catalyst                                Example                                                                              Example    (gms)     (gms)*    Molarity                                ______________________________________                                        48     17         60        209       0.5                                     49     18         65        110       0.26                                    50     19         66        109       0.26                                    51     20         66        109       0.3                                     ______________________________________                                         *Amount charged; 25 mls. was removed in drying step.                     

The nylon block polymers prepared either by hand casting or reactioninjection molding in Examples 29-51 were tested for various propertiessubstantially in accordance with the following procedures:

    ______________________________________                                        Tensile Strength                                                                          ASTM D1708   [units are pounds per                                                         square inch (psi) or                                                          megapascals (MPa)].                                  Tear Strength                                                                             ASTM D1004   [units are pounds-force                                                       per linear inch (pli)                                                         or newtons per meter                                                          (N/m)].                                              Flexural Modulus                                                                          ASTM D790    [units are pounds per                                                         square inch (psi) or                                                          megapascals (MPa)].                                  Notched Izod                                                                              ASTM D256    [units are foot-pounds                               Impact                   per inch notch                                                                (ft. lbs./in.) or joules                                                      per meter (J/m)].                                    ______________________________________                                    

Test results for Examples 29-51 are provided in Table F. Tensileelongation (to break) determined in accordance with ASTM D 1708 forthese nylon block polymers was generally greater than 50% and in somecases greater than 200%.

                                      TABLE F                                     __________________________________________________________________________    NYLON BLOCK POLYMER PROPERTIES                                                     Tensile                                                                              Tear       Flexural  Izod                                         Polymer                                                                            Strength                                                                             Strength   Modulus   Impact                                       Example                                                                            psi                                                                              (MPa)                                                                             pli                                                                              (N/m × 10.sup.-3)                                                               psi × 10.sup.-3                                                               (MPa)                                                                             ft. lbs./in.                                                                        (J/m)                                  __________________________________________________________________________    29   6060                                                                             (41.7)                                                                            1660                                                                             (291)   200   (1379)                                                                            11.8  (630)                                  30   5930                                                                             (40.8)                                                                            1410                                                                             (247)   222   (1531)                                                                            12.0  (641)                                  31   6190                                                                             (42.6)         219   (1510)                                                                            11.3  (603)                                  32   6570                                                                             (45.3)         167   (1151)                                                                            9.4   (502)                                  33   6030                                                                             (41.5)         218   (1503)                                                                            8.9   (475)                                  34   6060                                                                             (41.7)         185   (1276)                                                                            19.9  (1062)                                  35* 8060                                                                             (55.5)         334   (2303)                                                                            3.3   (176)                                  36   6740                                                                             (46.4)                                                                            1570                                                                             (275)   223   (1538)                                                                            3.6   (192)                                  37   6300                                                                             (43.4)                                                                            1550                                                                             (271)   250   (1724)                                                                            10.5  (560)                                  38   6020                                                                             (41.5)                                                                            1580                                                                             (277)   215   (1482)                                                                            11.4  (609)                                  39   6790                                                                             (46.8)         240   (1655)                                                                            5.1   (272)                                  40   5780                                                                             (39.8)         183   (1262)                                                                            2.5   (133)                                  41   6810                                                                             (46.9)                                                                            1240                                                                             (217)   213   (1469)                                                                            12.0  (641)                                  42   6100                                                                             (42.0)                                                                            1350                                                                             (236)   189   (1303)                                                                            8.0   (427)                                  43   5270                                                                             (36.3)                                                                             800                                                                             (140)    58    (400)                                                                            22.0  (1174)                                 44   6260                                                                             (43.1)                                                                            1200                                                                             (210)   228   (1572)                                                                            3.0   (160)                                  45   6520                                                                             (44.9)                                                                            1290                                                                             (226)   178   (1227)                                                                            12.1  (646)                                  46   5990                                                                             (41.3)                                                                            1430                                                                             (250)   211   (1455)                                                                            1.8    (96)                                  47   6100                                                                             (42.0)                                                                            1360                                                                             (238)   223   (1538)                                                                            1.8    (96)                                  48   6680                                                                             (46.0)                                                                            1330                                                                             (233)   210   (1448)                                                                            7.8   (416)                                  49   6530                                                                             (45.0)                                                                            1140                                                                             (200)   129    (889)                                                                            18.3  (977)                                  50   6950                                                                             (47.9)                                                                            1290                                                                             (226)   173   (1193)                                                                            19.9  (1062)                                 51   6740                                                                             (46.4)                                                                            1160                                                                             (203)   160   (1103)                                                                            17.6                                         __________________________________________________________________________     *Polymer was reinforced with 25% (wt.) P117B 1/16" milled glass fiber         (OwensCorning).                                                          

EXAMPLES 52-117

Examples 52-117 demonstrate the unexpected results exhibited by nylonblock copolymers prepared from acid halide functional or acyllactamfunctional material containing either polyether segments having minimummolecular weights of about 2,000 or polyester segments containingpolyether segments having minimum molecular weights of about 2,000.

A. Preparation Acyllactam Functional Materials

Acid halide functional materials were prepared from the polyetherslisted below in Table G. The preparation of these acid halide functionalmaterials involved preparing solutions of the desired polyether andterephthaloyl chloride in tetrahydrofuran. A sufficient quantity of anacid scavenger, triethylamine, was added to each solution, so as toprecipitate out of the solutions white amine hydrochloride. The molarquantities of the particular polyether (PE) and terephthaloyl chloride(TERE) used for each solution are shown in Table H.

For each particular polyether different acid halide functional materialswere prepared. In each case, acid halide functional materials containingpolyether segments and acid halide functional materials containingpolyester segments (comprising the polyether segment) were prepared.These polyester segments were formed by the linkage of polyethersegments with terephthaloyl chloride residues. Acid halide functionalmaterials containing polyether segments were prepared from mole ratiosof 2:1 for diol derivatives and 3:1 for triol derivatives, while thosematerials containing polyester segments were prepared from mole ratiosof 4:3 for diol derivatives and 5:2 for triol derivatives. These acidhalide to polyether mole ratios are listed in the following tables underthe heading AH/PE.

It should be noted that polymeric materials generally exist as mixturesor compositions containing species having varying molar amounts ofpolyether segments and acid halide residues. Thus, the molar ratio givenpertains to the amounts of materials used to prepare each mixture andthe average molar amount of acid halide residue to polyether residuefound for the species formed.

Batches of acyllactam functional materials were formed by adding to eachsolution of acid halide functional material a solution of caprolactamand triethylamine (an acid scavenger) in tetrahydrofuran. The molarquantity of caprolactam used for each batch is shown below in Table H.

The addition of the caprolactam solution to the solution of acid halidefunctional material was accomplished over a period of about 7 minutes.Each solution was heated to reflux at 76° C. and maintained as such forabout 1 hour. The solutions were then allowed to cool and about 100 ml.of tetrahydrofuran was added to each. Each batch was then filtered andwashed with more tetrahydrofuran (about 2 washings of 75 ml.). Theremaining tetrahydrofuran was then removed under vacuum at 80° C. over aperiod of about 3 hours.

The IR spectrum of Batch 1 showed no hydroxyl absorption but a strongester carbonyl absorption with a weaker amide carbonyl absorption. Thisconfirmed the preparation of the acyllactam functional material.

                  TABLE G                                                         ______________________________________                                        Polyethers                                                                    Designation       Description                                                 ______________________________________                                        Pluracol P1010 (P1010)                                                                          poly(oxypropylene) diol                                                       (Molec. wt. about 1,000)                                    Voranol 2010 (2010)                                                                             poly(oxypropylene) diol                                                       (Molec. wt. about 2,000)                                    PPG 3025 (PPG3025)                                                                              poly(oxypropylene) diol                                                       (Molec. wt. about 3,000)                                    PPG 4025 (PPG4025)                                                                              poly(oxypropylene) diol                                                       (Molec. wt. about 4,000)                                    Thanol SF 3950 (SF3950)                                                                         ethylene oxide capped                                                         poly(oxypropylene) diol                                                       (Molec. wt. about 3,500                                                       with the functionality of                                                     the composition being about                                                   2.1)                                                        Voranol CP2070 (CP2070)                                                                         poly(oxypropylene) triol                                                      (Molec. wt. about 725)                                      Voranol CP1500 (CP1500)                                                                         poly(oxypropylene) triol                                                      (Molec. wt. about 1,600)                                    Pluracol GP3030 (GP)                                                                            poly(oxypropylene) triol                                                      (Molec. wt. about 3,000)                                    Niax 11-34 (NIAX) ethylene oxide capped                                                         poly(oxypropylene) triol                                                      (Molec. wt. about 4,800)                                    Thanol SF6503 (SF6503)                                                                          ethylene oxide capped                                                         poly(oxypropylene) triol                                                      (Molec. wt. about 6,200)                                    Pluracol P-380 (P380)                                                                           ethylene oxide capped                                                         poly(oxypropylene) triol                                                      (Molec. wt. about 6,760)                                    ______________________________________                                    

                  TABLE H                                                         ______________________________________                                        Batch Poly-    AH/    Polyether                                                                              TERE   Caprolactam                             No.   ether    PE     (PE) (Moles)                                                                           (Moles)                                                                              (Moles)                                 ______________________________________                                         1    P1010    2:1    (0.468)  (0.936)                                                                              (0.973)                                  2             4:3    (0.468)  (0.624)                                                                              (0.327)                                  3    V2010    2:1    (0.251)  (0.502)                                                                              (0.504)                                  4             4:3    (0.251)  (0.335)                                                                              (0.177)                                  5    PPG3025  2:1    (0.171)  (0.342)                                                                              (0.354)                                  6             4:3    (0.171)  (0.228)                                                                              (0.124)                                  7    PPG4025  2:1    (0.120)  (0.240)                                                                              (0.242)                                  8             4:3    (0.120)  (0.160)                                                                              (0.097)                                  9    SF3950   2:1    (0.152)  (0.303)                                                                              (0.318)                                 10             4:3    (0.152)  (0.202)                                                                              (0.106)                                 11    CP2070   3:1    (0.450)  (1.350)                                                                              (1.360)                                 12             5:2    (0.450)  (1.125)                                                                              (0.909)                                 13    CP1500   3:1    (0.250)  (0.750)                                                                              (0.7575)                                14             5:2    (0.250)  (0.625)                                                                              (0.555)                                 15    GP       3:1    (0.160)  (0.480)                                                                              (0.485)                                 16             5:2    (0.150)  (0.375)                                                                              (0.303)                                 17    NIAX     3:1    (0.11)   (0.33) (0.333)                                 18             5:2    (0.179)  (0.445)                                                                              (0.361)                                 19    SF6503   3:1    (0.08)   (0.24) (0.2424)                                20             5:2    (0.08)   (0.20) (0.162)                                 21    P380     3:1    (0.08)   (0.24) (0.2424)                                22             5:2    (0.08)   (0.20) (0.162)                                 23             3:1    (0.06)   (0.18) (0.1818)                                ______________________________________                                    

B. Preparation of Nylon Block Copolymers

Nylon block copolymers (NBC) were prepared by reacting each batch ofacyllactam functional material with caprolactam in the presence ofcatalyst, caprolactam magnesium bromide. The method used for combiningthese materials was a reaction injection molding. This technique is wellknown in the art and involves directing a stream of acyllactamfunctional materials dissolved in caprolactam and a stream of thecaprolactam magnesium bromide catalyst dissolved in caprolactam into aheated mold.

A catalyst solution was prepared for use in preparing each nylon blockcopolymer example, except Examples 84 and 87, by charging a 3,000 ml.flask, which was equipped with a stirrer, thermocouple-controlled heaterand nitrogen inlet and a distillation head, with 1,650 grams ofcaprolactam. The caprolactam was dried by distilling off 50 grams of thecaprolactam from the flask under a vacuum (using an oil pump to providea vacuum under 1 mm.) at a pot temperature of 125°-130° C. The vacuumwas released to a nitrogen atmosphere and the flask with the caprolactamcooled down to 75° C. All atmospheric pressure operations were performedunder nitrogen. Once the caprolactam was dried, 120 ml. of a 3 molarsolution of ethyl magnesium bromide in diethyl ether was added over a 10minute period while maintaining vigorous agitation. The solutiontemperature was maintained at 100° C. The evolved ethane and ether wereremoved by degassing under a vacuum (less than 1 mm.) for an hour at 90°C. The catalyst solution was maintained at 90° C. and 200 ml. portionswere drawn off for use to prepare each sample. The prepared catalystsolution had a molarity of 0.225.

Prepolymer solutions were prepared, except for Examples 84 and 87, bydissolving a prepolymer, which was an acyllactam functional materialprepared in accordance with earlier Batches 1-23, in caprolactam. Toeach sample solution 0.5 grams of Flectol H® antioxidant was added. Theprepolymer solutions were dried by distilling off 25 ml. of caprolactam.The sample solutions were cooled to 85° C.

In Example No. 84, the catalyst solution was prepared according to theprocedure described but using only 225 grams of caprolactam which wasdried by distilling off 25 grams. Nineteen (19) ml. of a 3 molarsolution grams of ethyl magnesium bromide was added to the caprolactamaccording to the procedure described above. The catalyst solution wasthen maintained at 90° C.

The acyllactam functional material of Batch No. 11 was not dissolved incaprolactam. Insteadd, 181 grams of acyllactam functional material wasinjection molded so as to obtain a 30% by weight of polyether in thefinal nylon block copolymer. 1.5 grams of Flectol H® antioxidant wasadded to the acyllactam functional material prior to injection molding.

In Example No. 87, the catalyst was prepared in the same manner andquantities as described above for Example 84 with the exception that 16ml. of a 3 molar solution of ethyl magnesium bromide was used.

Again the acyllactam solution was not dissolved in caprolactam but 159grams of the acyllactam functional material of Batch No. 12 was used.

The specific prepolymer batch number and the amount of prepolymer andcaprolactam employed in preparing the prepolymer solutions for each ofExamples 52-117 is shown in Table J.

                  TABLE J                                                         ______________________________________                                                          Amount Charge                                                                 Prepolymer Solution                                                % Polyether                                                                              Prepolymer                                                                              Prepolymer                                                                            Caprolactam                               Example                                                                              in Final NBC                                                                             Batch No. (gms)   (gms)*                                    ______________________________________                                        52     10         1         43      132                                       53     20         1         87      88                                        54     30         1         130     45                                        55     10         2         37      138                                       56     20         2         74      101                                       57     30         2         111     64                                        58     10         3         38      138                                       59     20         3         75      100                                       60     30         3         113     63                                        61     10         4         34      141                                       62     20         4         68      107                                       63     30         4         102     73                                        64     10         5         35      140                                       65     20         5         70      105                                       66     30         5         105     70                                        67     10         6         33      142                                       68     20         6         65      110                                       69     30         6         98      77                                        70     10         7         33      142                                       71     20         7         67      108                                       72     30         7         100     75                                        73     10         8         32      143                                       74     20         8         64      111                                       75     30         8         96      79                                        76     10         9         34      141                                       77     20         9         68      107                                       78     30         9         102     73                                        79     10         10        32      143                                       80     20         10        65      110                                       81     30         10        97      78                                        82     10         11        60      115                                       83     20         11        121     54                                        84     30         11        181     --                                        85     10         12        53      122                                       86     20         12        106     69                                        87     30         12        159     --                                        88     10         13        43      132                                       89     20         13        87      88                                        90     30         13        130     45                                        91     10         14        41      134                                       92     20         14        81      94                                        93     30         14        122     53                                        94     10         15        38      138                                       95     20         15        75      100                                       96     30         15        113     63                                        97     10         16        36      139                                       98     20         16        71      104                                       99     30         16        107     68                                        100    10         17        34      141                                       101    20         17        69      106                                       102    30         17        103     72                                        103    10         18        33      142                                       104    20         18        67      108                                       105    30         18        100     75                                        106    10         19        34      141                                       107    20         19        67      108                                       108    30         19        101     74                                        109    10         20        33      142                                       110    20         20        65      110                                       111    30         20        98      77                                        112    10         21        33      142                                       113    20         23        67      108                                       114    30         23        100     75                                        115    10         22        32      143                                       116    20         22        65      110                                       117    30         22        97      78                                        ______________________________________                                         *Amount charged; 25 ml. was removed in drying step.                      

The nylon block copolymers in Examples 52-83, 86, and 88-117 wereprepared by pumping the prepolymer solutions and the catalyst solutionin a 1:1 stream volume ratio into a closed mold heated to 140° C. havingan internal cavity of 20.32 cm.×20.32 cm.×3.175 cm. Examples 84 and 87were prepared by pumping the prepolymer and catalyst solution in a1.52:1 and 1.13:1 stream volume ratio, respectively, into a similarmold. Mixing of the combined streams prior to injection into the moldwas performed by means of an in-line 4 inch to one-quarter inch Kenicsstatic mixer. Examples 52-117 were then tested to determine their impactand flexibility properties substantially in accordance with thefollowing procedures: Flexural Modulus, Notched Izod Impact (which weredescribed above) and

Driven Dart: Procedure described in November 1974 SPE Retec Bulletin byV. A. Matonis--15.88 mm. (5/8 in.) diameter Dart driven at 111.76m./min. (4400 in./min.) impacted against a 3.2 mm. (1/8 in.) by 50.8 mm.(2 in.) diameter disc of the specific NBC which was held against a 31.75mm. (11/4 in.) sample ring at a temperature -29° C. (-20° F.). Energymeasurements made with a Nicolet 1094 Digital Oscilloscope [units arejoules (J) or inches per pounds (in.-lbs.)]

The test results are provided in Tables (K-1)-(K-4) below. The examplesare arranged according to polyether type (either diol or triolderivatives), percent by weight of polyether in the nylon blockcopolymer, and by the AH/PE ratio to highlight the effect of molecularweight upon impact properties.

                  TABLE K-1                                                       ______________________________________                                               Flexural     Izod         Driven                                       Example                                                                              Modulus      Impact       Dart                                         No.    MPa (psi × 10.sup.-3)                                                                J/m (ft.-lbs/in.)                                                                          J (in./lbs.)                                 ______________________________________                                        Diol Derivatives                                                              2:1 AH/PE Ratio                                                               10% Polyether                                                                 52     2268    (329)     21    (0.4) 0.3  (2.6)                               58     1517    (220)     64    (1.2) 2.1  (18.7)                              64     1972    (286)     69    (1.3) 0.9  (7.9)                               70     2462    (357)     91    (1.7) --   --                                  76     1855    (269)    133    (2.5) 8.3  (75.0)                              20% Polyether                                                                 53     1069    (155)     16    (0.3) 0.1  (1.1)                               59     1172    (170)    155    (2.9) 2.7  (24.6)                              65     1482    (215)    133    (2.5) 1.8  (16.4)                              71      979    (142)    294    (5.5) 2.6  (23.6)                              77     1248    (181)    731    (13.7)                                                                              13.7 (123.1)                             30% Polyether                                                                 54      310     (45)     16    (0.3)  1/4.01                                                                            (0.5)                               60     1220    (177)    475    (8.9) 7.9  (70.8)                              66      614     (89)    502    (9.4) 8.5  (76.1)                              72      455     (66)    384    (7.2) 12.1 (109.0)                             78      545     (79)    598    (11.2)                                                                              52.3 (470.2)                             ______________________________________                                    

                  TABLE K-2                                                       ______________________________________                                               Flexural     Izod         Driven                                       Example                                                                              Modulus      Impact       Dart                                         No.    MPa (psi × 10.sup.-3)                                                                J/m (ft.-lbs/in.)                                                                          J (in./lbs.)                                 ______________________________________                                        Triol Derivatives                                                             3:1 AH/PE Ratio                                                               10% Polyether                                                                  82    2165    (314)     16    (0.3) 0.1  (1.2)                                88    2144    (311)     75    (1.4) 0.6  (5.5)                                94    1889    (274)     80    (1.5) 2.9  (26.1)                              100    1441    (209)    155    (2.9) 8.4  (75.7)                              106    1717    (249)    342    (6.4) 19.1 (172.0)                             112    1703    (247)    352    (6.6) 8.2  (73.9)                              20% Polyether                                                                  83     331     (48)     5     (0.1) 1/4.1                                                                              (0.1)                                89     924    (134)     48    (0.9) 0.1  (2.1)                                95    1331    (193)    774    (14.5)                                                                              23.8 (214.0)                             101    1020    (148)    961    (18.0)                                                                              59.2 (531.8)                             107    1096    (159)    838    (15.7)                                                                              30.7 (275.4)                              113A   745    (108)    715    (13.4)                                                                              55.7 (500.3)                             .sup. 113B                                                                            731    (106)                 34.4 (308.8)                             30% Polyether                                                                  84    (Poor Reactivity)                                                       90     407     (59)    165    (3.1) 0.1  (0.8)                                96     414     (60)    630    (11.8)                                                                              20.5 (184.1)                             102     415    (60.2)   667    (12.5)                                                                              22.3 (200.3)                             108     421     (61)    619    (11.6)                                                                              26.7 (239.9)                             114     393     (57)    582    (10.9)                                                                              26.3 (236.2)                             ______________________________________                                    

                  TABLE K-3                                                       ______________________________________                                               Flexural     Izod         Driven                                       Example                                                                              Modulus      Impact       Dart                                         No.    MPa (psi × 10.sup.-3)                                                                J/m (ft.-lbs/in.)                                                                          J (in./lbs.)                                 ______________________________________                                        Diol Derivatives                                                              4.3 AH/PE Ratio                                                               10% Polyether                                                                 55     1848    (268)     48    (0.9) 2.3  (20.5)                              61     2517    (365)     48    (0.9) --   --                                  67     2213    (321)     59    (1.1) --   --                                  73      799    (113)     32    (0.6) --   --                                  79     1951    (283)     64    (1.2) 1.3  (12.0)                              20% Polyether                                                                 56     1254    (182)    101    (1.9) 2.4  (21.8)                              62     1282    (186)    107    (2.0) 5.9  (53.1)                              68     1400    (203)    160    (3.0) 16.9 (151.9)                             74     1034    (149)    214    (4.0) 9.6  (86.3)                              80     1220    (177)    657    (12.3)                                                                              29.6 (266.1)                             30% Polyether                                                                 57      752    (109)    128    (2.4) 2.1  (18.9)                              63      703    (102)    673    (12.6)                                                                              23.0 (207.0)                             69     1069    (155)    731    (13.7)                                                                              34.5 (310.0)                             75      455     (66)    139    (2.6) 6.2  (55.7)                              81       421    (61)    432    (8.1) 36.4 (327.2)                             ______________________________________                                    

                  TABLE K-4                                                       ______________________________________                                               Flexural     Izod         Driven                                       Example                                                                              Modulus      Impact       Dart                                         No.    MPa (psi × 10.sup.-3)                                                                J/m (ft.-lbs/in.)                                                                          J (in./lbs.)                                 ______________________________________                                        Triol Derivatives                                                             5:2 AH/PE Ratio                                                               10% Polyether                                                                  85    2082    (302)     48    (0.9) 2.4  (2.1)                                91    1641    (238)    101    (1.9) 2.7  (24.0)                               97    1531    (222)     96    (1.8) 4.0  (35.8)                              103    2006    (291)     96    (1.8) 3.1  (28.3)                              109    1696    (246)    246    (4.6) 10.6 (95.6)                              115    1607    (233)    128    (2.4) 4.0  (35.5)                              20% Polyether                                                                  86     565     (82)     11    (0.2) .01  (0.7)                                92    1103    (160)    256    (4.8) .05  (4.3)                                98    1227    (178)    230    (4.3) 10.8 (96.9)                              104    1145    (166)    731    (13.7)                                                                              34.2 (307.2)                             110    1041    (151)    741    (14.0)                                                                              50.1 (449.9)                             116    1207    (175)    747    (14.0)                                                                              29.3 (263.4)                             30% Polyether                                                                  87     283     (41)     21    (0.4) 1/4.01                                                                             (0.4)                                93     452    (65.5)   470    (8.8) 0.6  (5.0)                                99     556    (80.6)   785    (14.7)                                                                              19.1 (171.5)                             105     607     (88)    689    (12.9)                                                                              23.6 (212.4)                             111     503     (73)    662    (12.4)                                                                              31.7 (285.0)                             117     448     (65)    523    (9.8) 28.2 (253.5)                             ______________________________________                                    

As indicated in Table (K-1)-(K-4), the impact property test results,i.e. Izod Impact and Driven Dart, of nylon block copolymers containingpolyether segments or polyester segments having polyether segmentsexhibit unexpected results when the polyether segments have a minimummolecular weight of about 2,000. For example, see Examples 52-57 and82-87 which contained polyether segments with molecular weights of 1,000and 725, respectively, exhibited significantly lower impact propertiesthan the remaining examples wherein the molecular weights were at about2,000 or more. Examples 89-90 and 91-93 exhibited better impactproperties and were prepared from polyether segments derived from triolshaving a minimum molecular weight of about 1,600 which is within thepreferred minimum molecular weight of about 2,000. The effect is moreapparent at polyether contents greater than 10 weight percent of thenylon block copolymer, most likely due to the greater influence of thepolyamide segments than the polyether segments at such low levels ofpolyether in the nylon block copolymer.

Furthermore, as indicated in Table K, the impact property test resultsof nylon block copolymers containing polyether segments and polyestersegments having polyether segments, exhibit unexpected results when thepolyethers were derived from triols as compared diols, see Examples94-96 and 97-99 for triol derivatives and Examples 64-66 and 67-69 fordiol derivatives. Both the triols and diols utilized had molecularweights of about 3,000.

Also as stated above, a minimum amount of cross-linking in thecomposition results in better properties. This is seen by comparing theimpact properties of those nylon block copolymers prepared from PPG 4025(Examples 70-72 and 73-75) with those prepared from Thanol SF 3950(Examples 76-78 and 79-81). Thanol SF 3950 was a composition having afunctionality of about 2.1, thus allowing for some minimalcross-linking. It should be noted that while the Examples demonstratepolyethers having a functionality greater than two, this association offunctionality and improved impact would also be applicable forpolysiloxanes and hydrocarbons.

Examples 118-122

Examples 118-122 were prepared to demonstrate the effect of specific Rgroups had upon impact and other properties of nylon block copolymersmade from prepolymers containing such R groups hereinabove described(see Formula I(a)).

As discussed above, preferred R groups are hydrocarbon groups andhydrocarbon groups having ether linkages which provide at least threesuccessively bonded elementary atoms between any two carbonyl groupsbonded to R. Acyllactam functional materials were made by reacting apolyether (NIAX) with various acid halides, as specified in Table Lbelow. Some of the acid halides used (i.e. o-phthalic acid chloride andfumaric acid chloride) formed R groups that provided less than 3successively bonded atoms between the two carbonyl groups. The remaininghalides formed forming R groups providing 3 or more successively bondedatoms between 2 carbonyl groups. The resulting acid halide functionalmaterials were then reacted with caprolactam (the specific process ofpreparing these materials is similar to the process describedhereinabove and will not be discussed in detail herein) to form lactamfunctional materials. These acyllactam functional materials were blendedinto caprolactam and then reacted with a catalyst-caprolactam solution(prepared according to a process similar to the process described above)to form nylon block copolymers having 20 weight percent polyethercontent. The resulting nylon block copolymers were subjected to thefollowing tests: Driven Dart (described above) and

Acetone Extractables: Percent weight loss after 24 hours in a SoxhletExtractor.

                  TABLE L                                                         ______________________________________                                                                Driven     Acetone                                    Example Acid            Dart       Extractable                                No.     Halide          J (in./lbs.)                                                                             (%)                                        ______________________________________                                        118     m-phthalic acid chloride                                                                      (316.7)    1.64                                       119     p-phthalic acid chloride                                                                      (141.1)    1.76                                       120     o-phthalic acid chloride                                                                       (1.8)     3.38                                       121     sebacic acid chloride                                                                         (315.2)    1.71                                       122     fumaric acid chloride                                                                          (1.1)     34.0                                       ______________________________________                                    

As seen from Table L, the impact properties (Driven Dart) of a nylonblock copolymer are improved when the R group provides at least threesuccessively bonded atoms between any two carbonyl groups bonded to theR group, see Examples 118, 119, and 121.

While the preferred embodiments of the present invention have beendescribed and illustrated, various modifications or substitutions can bemade thereto without departing from the spirit and scope of theinvention. Accordingly, it is to be understood that the presentinvention has been described by way of illustration and not limitation.

We claim:
 1. A process for preparing a nylon block copolymer which comprises bringing together and reacting lactam monomer, basic lactam polymerization catalyst and a lactam functional material of the formula: ##STR18## wherein: Q is ##STR19## with Y equal to C₃ -C₁₁ alkylene; b is an integer equal to 2 or more;R₁ is an alkyl, aryl, aralkyl, halogen alkyloxy, aryloxy, or aralkyloxy group; Z is a segment of: (1) a polyether, provided said polyether is not solely polyarylene polyether; (2) a polyester containing polyether or polymeric hydrocarbon segments; (3) a hydrocarbon; (4) a polysiloxane; or (5) mixtures thereof.
 2. The process of claim 1 wherein Z is a segment of:(1) a polyether derived from the triols; or (2) a polyester containing polyether segments derived from a triol.
 3. The process of claim 2 wherein Z is a segment of:(1) a polyether derived from the triol having a minimum molecular weight of about 3,000; or (2) a polyester containing polyether segments derived from the triol having minimum molecular weights of about 3,000.
 4. The process of claim 1 wherein Z is a segment of:(1) a polyether derived from a tetrol; or (2) a polyester containing a polyether segment derived from a tetrol.
 5. The process of claim 4 wherein Z is a segment of:(1) a polyether derived from a tetrol having a minimum molecular weight of about 4,000; or (2) a polyester containing polyether segments derived from the tetrol having minimum molecular weights of about 4,000.
 6. The process of claim 1 wherein the polyether segment comprises poly(oxyethylene), poly(oxybutylene), poly(oxypropylene), or a block copolymer of poly(oxypropylene) and poly(oxyethylene).
 7. The process of claim 3 wherein the polyether segments comprise poly(oxyethylene), poly(oxybutylene), poly(oxypropylene), or a block polymer of poly(oxypropylene) and poly(oxyethylene).
 8. The process of claim 5 wherein the polyether segments comprise poly(oxyethylene), poly(oxybutylene), poly(oxypropylene), or a block polymer of poly(oxypropylene) and poly(oxyethylene).
 9. The process of claim 1 wherein Q is a residue of caprolactam.
 10. The process of claim 3 wherein Q is a residue of caprolactam.
 11. The process of claim 1 wherein said basic lactam polymerization catalyst is provided in an effective amount to result in substantial completion within ten minutes of polymerization of the lactam monomer and lactam functional material to form the nylon block polymer in a molded shape.
 12. The process of claim 3 wherein said basic lactam polymerization catalyst is provided in an effective amount to result in substantial completion within ten minutes of polymerization of the lactam monomer and lactam functional material to form the nylon block polymer in a molded shape.
 13. The process of claim 5 wherein said basic lactam polymerization catalyst is provided in an effective amount to result in substantial completion within ten minutes of polymerization of the lactam monomer and lactam functional material to form the nylon block polymer in a molded shape.
 14. The process of claim 9 wherein said basic lactam polymerization catalyst is provided in an effective amount to result in substantial completion within ten minutes of polymerization of the lactam monomer and lactam functional material to form the nylon block polymer in a molded shape.
 15. The process of claim 11 which is carried out at a temperature of from about 70° C. to about 250° C.
 16. The process of claim 12 which is carried out at a temperature of from about 70° C. to about 250° C.
 17. The process of claim 13 which is carried out at a temperature of about 70° C. to about 250° C.
 18. The process of claim 14 which is carried out at a temperature of from about 70° C. to about 250° C.
 19. The process of claim 1 which is carried out at a temperature of from about 70° C. to about 250° C.
 20. The process of claim 1 which is carried out at a temperature of from about 120° C. to about 170° C.
 21. The process of claim 11 which is carried out at a temperature of from about 120° C. to about 170° C.
 22. The process of claim 12 which is carried out at a temperature of from about 120° C. to about 170° C.
 23. The process of claim 13 which is carried out at a temperature of from about 120° C. to about 170° C.
 24. The process of claim 1 wherein the catalyst is caprolactam magnesium bromide or chloride.
 25. The process of claim 15 wherein the catalyst is caprolactam magnesium bromide or chloride.
 26. The process of claim 16 wherein the catalyst is caprolactam magnesium bromide or chloride.
 27. A process for preparing a nylon block copolymer which comprises bringing together and reacting lactam monomer, basic lactam polymerization catalyst and a composition comprising the reaction products of lactam monomer and acid halide functional materials selected from the group represented by the formula: ##STR20## wherein: X is a halide;b is an integer equal to 2 or more; R₁ is an alkyl, aryl, aralkyl, alkyloxy, aryloxy, aralkyloxy, or halogen group; and Z is a segment of: (1) a polyether having a minimum molecular weight of about 2000; (2) a polyester containing polyether segments having minimum molecular weights of about 2000; (3) a polyester containing polymeric hydrocarbon segments having minimum molecular weights of about 500 to about 4,000; (4) a hydrocarbon; (5) a polysiloxane; or (5) combinations thereof,wherein said composition is essentially free of basic lactam polymerization catalyst or residue thereof.
 28. The process of claim 27 wherein the polymeric hydrocarbon segments of the polyester segments are polybutadiene segments.
 29. A process for preparing a nylon block copolymer which comprises bringing together and reacting lactam monomer, basic lactam polymerization catalyst and a composition containing one or more lactam functional materials selected from the group represented by the formula: ##STR21## wherein; Q is ##STR22## with Y equal to C₃ -C₁₁ alkylene; b is an integer equal to 2 or more;R₁ is an alkyl, aryl, aralkyl, alkyloxy, aryloxy, or aralkyloxy group; and Z is a segment of: (1) a polyether; (2) a polyester containing polyether or polymeric hydrocarbon segments; (3) a hydrocarbon; (4) a polysiloxane; or (5) combinations thereof,wherein said composition is essentially free of basic lactam polymerization catalyst or residue thereof.
 30. The process of claim 29 wherein Q is a residue of caprolactam.
 31. The process of claim 28 wherein Q is a residue of caprolactam.
 32. The process of claim 29 wherein said basic lactam polymerization catalyst is provided in an effective amount to result in substantial completion within ten minutes of polymerization of the lactam monomer and lactam functional material to form the nylon block polymer in a molded shape.
 33. The process of claim 28 wherein said basic lactam polymerization catalyst is provided in an effective amount to result in substantial completion within ten minutes of polymerization of the lactam monomer and lactam functional material to form the nylon block polymer in a molded shape.
 34. The process of claim 30 wherein said basic lactam polymerization catalyst is provided in an effective amount to result in substantial completion within ten minutes of polymerization of the lactam monomer and lactam functional material to form the nylon block polymer in a molded shape.
 35. The process of claim 31 wherein said basic lactam polymerization catalyst is provided in an effective amount to result in substantial completion within ten minutes of polymerization of the lactam monomer and lactam functional material to form the nylon block polymer in a molded shape.
 36. The process of claim 1 wherein the Z segment is: (1) a hydrocarbon having a molecular weight of about 500 to about 4000; or (2) a polyester containing polymeric hydrocarbon segments having molecular weights of about 500 to about
 4000. 37. The process of claim 36 which is carried out at a temperature of from about 70° C. to about 250° C.
 38. A process for preparing a nylon block copolymer which comprises bringing together and reacting lactam monomer, basic lactam polymerization catalyst and a composition containing one or more lactam functional materials selected from the group represented by the formula: ##STR23## wherein, Q is ##STR24## with Y equal to C₃ -C₁₁ alkylene; b is an integer equal to 2 or more;R₁ is an alkyl, aryl, aralkyl, alkyloxy, aryloxy, or aralkyloxy group; and Z is a segment of: (1) a polyether provided said polyether is not solely polyarylene polyether; (2) a polyester containing polyether or polymeric hydrocarbon segments; (3) a hydrocarbon; (4) a polysiloxane; or (5) combinations thereof, the materials being substantially the only lactam functional materials in said composition.
 39. The process of claim 38 wherein b is greater than
 2. 40. The process of claim 38 wherein the average value of b for all the acyllactam functional materials in said composition is greater than two.
 41. The process of claim 38 which is carried out at a temperature of from about 70° C. to about 250° C.
 42. The process of claim 41 which is carried out at a temperature of from about 120° C. to about 170° C.
 43. The process of claim 39 which is carried out at a temperature of from about 70° C. to about 250° C.
 44. The process of claim 29 which is carried out at a temperature of from about 70° C. to about 250° C.
 45. The process of claim 32 which is carried out at a temperature of from about 70° C. to about 250° C.
 46. The process of claim 33 which is carried out at a temperature of from about 70° C. to about 250° C.
 47. The process of claim 36 which is carried out at a temperature of from about 120° C. to about 170° C.
 48. The process of claim 39 which is carried out at a temperature of from about 120° C. to about 170° C.
 49. The process of claim 29 which is carried out at a temperature of from about 120° C. to about 170° C.
 50. The process of claim 32 which is carried out at a temperature of from about 120° C. to about 170° C.
 51. The process of claim 29 wherein the catalyst is caprolactam magnesium bromide or chloride.
 52. The process of claim 39 wherein the catalyst is caprolactam magnesium bromide or chloride.
 53. The process of claim 36 wherein the catalyst is caprolactam magnesium bromide or chloride.
 54. The process of claim 1 wherein b is greater than
 2. 55. The process of claim 36 wherein b is greater than
 2. 56. The process of claim 36 wherein b is three or four.
 57. A process for preparing a nylon block copolymer which comprises bringing together and reacting lactam monomer, basic lactam polymerization catalyst and a lactam functional material of the formula: ##STR25## wherein: Q is ##STR26## with Y equal to C₃ -C₁₁ alkylene; b is an integer equal to 2 or more;R₁ is an alkyl, aryl, aralkyl, halogen alkyloxy, aryloxy, or aralkyloxy group; Z is a segment of: (1) a polyether having a minimum molecular weight of about 2000; or (2) a polyester containing polyether segments having minimum molecular weights of about
 2000. 58. The process of claim 57 wherein the polyether segment comprises poly(oxyethylene), poly(oxybutylene), poly(oxypropylene), or a block copolymer of poly(oxypropylene) and poly(oxyethylene).
 59. The process of claim 57 wherein Q is a residue of caprolactam.
 60. The process of claim 58 wherein Q is a residue of caprolactam.
 61. The process of claim 57 wherein said basic lactam polymerization catalyst is provided in an effective amount to result in substantial completion within ten minutes of polymerization of the lactam monomer and lactam functional material to form the nylon block polymer in a molded shape.
 62. The process of claim 58 wherein said basic lactam polymerization catalyst is provided in an effective amount to result in substantial completion within ten minutes of polymerization of the lactam monomer and lactam functional material to form the nylon block polymer in a molded shape.
 63. The process of claim 59 wherein said basic lactam polymerization catalyst is provided in an effective amount to result in substantial completion within ten minutes of polymerization of the lactam monomer and lactam functional material to form the nylon block polymer in a molded shape.
 64. The process of claim 60 wherein said basic lactam polymerization catalyst is provided in an effective amount to result in substantial completion within ten minutes of polymerization of the lactam monomer and lactam functional material to form the nylon block polymer in a molded shape.
 65. The process of claim 57 which is carried out at a temperature of from about 70° C. to about 250° C.
 66. The process of claim 58 which is carried out at a temperature of from about 70° C. to about 250° C.
 67. The process of claim 61 which is carried out at a temperature of from about 70° C. to about 250° C.
 68. The process of claim 62 which is carried out at a temperature of from about 70° C. to about 250° C.
 69. The process of claim 63 which is carried out at a temperature of from about 70° C. to about 250° C.
 70. The process of claim 57 which is carried out at a temperature of from about 120° C. to about 170° C.
 71. The process of claim 58 which is carried out at a temperature of from about 120° C. to about 170° C.
 72. The process of claim 53 which is carried out at a temperature of from about 120° C. to about 170° C.
 73. The process of claim 62 which is carried out at a temperature of from about 120° C. to about 170° C.
 74. The process of claim 57 wherein the catalyst is caprolactam magnesium bromide or chloride.
 75. The process of claim 57 wherein the catalyst is caprolactam magnesium bromide or chloride.
 76. The process of claim 53 wherein the catalyst is caprolactam magnesium bromide or chloride.
 77. The process of claim 57 wherein b is greater than two.
 78. The process of claim 29 wherein Z is a segment of: (1) a polyether derived from a triol; or (2) a polyester containing polyether segments derived from a triol.
 79. The process of claim 29 wherein Z is a segment of: (1) a polyether derived from a triol having a minimum molecular weight of about 3,000; or (2) a polyester containing polyether segments derived from a triol having minimum molecular weights of about 3,000.
 80. The proess of claim 29 wherein Z is a segment of: (1) a polyether having a minimum molecular weight of about 2,000; or (2) a polyester containing polyether segments having minimum molecular weights of about 2,000.
 81. The process of claim 80 wherein Q is the residue of caprolactam.
 82. The process of claim 38 wherein said basic lactam polymerization catalyst is provided in an effective amount to result in substantial completion within ten minutes of polymerization of the lactam monomer and lactam functional material to form the nylon block polymer in a molded shape. 